Scope of tlic cliapter

?liis chapter gives a 6rief &sniption of the general metha3 emphyedfor

the charact&ation of different types of reactive palm 6 h d , th&$fier
reinforcedcomposites andvarious ctiemicalj a n d m a t d usedfor theirprocessing.
llie metha3 emplbyed for the detenninatwn of physical; chemical; mechanical;
thenno-a~lytidadr/ieo&icaCprop&ies of the matt&resins andpolynrer 6 b d
are d i s u s e d cL)Iffmnt technems used for the optimization of process conditions
of the matt& resins and composites are also eqbined: 6rief account of the
speafi. methds adbptedfor the qua% evalition of the crosslin@d neat resins
and t h i r lhminates is given -mu mechanicaland th-mechanicalanaCyses
of the diffkent systems are discussed: ;4 6&f &scription of the fracture suzface
ana&it caniedout on composites at different h e h of modifiation using scanning
elkctron microscopy is included:3 ht of the diffmnt stanrihrdtecfiniques emphyed
for the characterization of the composite materiaLF is &ogiven
 This chapter gives a brief description of the general methods employed for the
characterisation of different types of reactive polymer blends, their composites and
various chemicals and materials used for their development. The methods employed
for the determination of physical, chemical, chromatographic, mechanical, thermo-
analytical and rheological properties of the matrix resins and polymer blends are
discussed. Various techniques adopted for the optimization of process conditions of
the matrix resins and composites are also explained. The specific methods adopted
for the quality evaluation of the crosslinked neat resins and their composites are also
highlighted.

2.1 Materials
The materials used for the study, their sources and properties are given in Table 2.1

Table 2.1 Materials properties and sources

Diallyl bisphenol A (DABA) Synthesized in house from b i e n o l A by a known '
procedure'.
Epoxyresin, EPN 1139 Supplied by MIS Ciba Geigy, Mumbai, epoxy
equivalent weight 185.2
Epoxy resin, Ly-556 Supplied by MIS Ciba Geigy. Mumbai, epoxy
equivalent weight 181.2
Epoxy resin, Tri epoxy Procured from MISAldrich. USA, eq. weight 153.3
Triphenylphosphine (TPP) Supplied by MISE-Merck, molecular weight 285
Bismaleimide (BMIP) Synthesized in VSSC by a repotted procedure
Bismaleimide (BMIM) Supplied by MISSigma Aldrich, USA
Bismaleimide (BMIE) Synthesized in PSCD,VSSC by a standard procedureJ
E-Glass cloth Plain weave. Silane treated, thickness
0.25mm from M/s Unnathi Corporatiin, India
Plane weave Carbon cloth T- 300 grade, Supplied by MISTorray. Japan
Satin weave Carbon cloth T- 300 grade, Supplied by MISTorray. Japan
 Chapter 2 95

2.2 Characterization Techniques

The different standard techniques employed for the characterization of the
composite materials and their constituents are given in Table.2.2

Table 2.2 Standard test procedures used for material characterization

Standard procedures Reference
Mechanical Properties
Tensile strength ASTM D 3039 M-00
Compressive strength ASTM D-3379-75
Flexural strength ASTM D 790 M-86
Inter laminar shear strength ASTM D 2344-84
Interfacial shear strength ASTM D-3846-02
Fracture Toughness ASTM D-30-02-87
1
I

Fatigue resistance I ASTM D-3479-76

I
Lap shear strength ASTM D-1002-01
Dynamic mechanical properties I ASTM D-4092-82
Thermal Properties
Thermal Stability ASTM D-3850-82
Linear Expansion ASTM E-831-81
Glass transition Temperature ASTM D-3418-82
Cure reaction Temperatures ASTM E- 793-81
Specific heat ASTM D-3947-86
-
Physical Properties
-
Water absorption ASTM D-570-98
Density ASTM D-792-66
Constituent content ASTM D 3171-99
Void content ASTM D-2734-94
Chapter 2 96

2.2.1 Spectroscopic Analysis

Fourier Transform Infrared Spectroscopy (FTIR) was employed for the cure
characterization of the matrix system. Samples were scanned for characteristic
functional group absorptions in a PerkinElmer Spectrum GXA FTIR
spectrophotometer for a wave length range of 4000-650 cm-I. The instrument
employed a pyroelechic detector and each interferogram was genefated by signal
averaging of 32 scans at a resolution of 4cm-1. The resin samples were smeared
between two NaCl plates to form a thin film for recording the spectrum. Solid samples
were powdered and pelletised with KBr for the analysis. The spectra were obtained as
percentage transmittance versus wave number.

2.2.2 Rheological characterization

Rheological characterization of the matrix system was carried out for the
optimization of its cure conditions and to fix the processing window of the neat resin
and laminate. The rheologkal analysis was done with a Reologica Stress Tech
Rheometer. The instrument was used in the oscillation mode using a parallel plate
assembly (20 mm dia) with a gap of 0.5mm in a controlled strain mode. The storage
shear modulus G', Loss shear modulus G*and complex viscosity 11' are measured as
a function of temperature. Isothermal rheological studies were also carried out by
recording the above parameters as a function of time at the required fixed
temperatures.

2.2.3 Gel Permeation Chromatography

Molecular weights and molecular weight distributions of the pdymer samples
were determined using Waters model 2690 Alliance Gel Permeation Chromatograph
(GPC). The chromatorgrams were recorded using four microstyragel columns lo4 A-,
loSA', 500 A' and 100 A', calibrated with polystyrene standards using the universal
Chapter 2 97

calibration method. Differential refractive index (DRI-R401) and UV detectors were

employed for the analysis 4. Tetrahydrofuran (THF) was used as the solvent at a flow
rate of 2mllmin. Number average (M,) and molecular weight distribution of the
polymer samples were obtained from the chromatograms.

2.2.4 Thermal Analysis

The major thermal analysis techniques used for the thermal characterization
of the matrix resin compositions, composites and their raw materials are Differential
Thermal Analysis-DTA, Differential Scanning Calorimetry (DSC), Thermo gravimetnc
Analysis (TGA). Thermo Mechanical Analysis (TMA) and Dynamic Mechanical
Thermal Analysis (DMTA).
2.2.4.1 Differential Scanning Calorimetry
Thermo-analytical techniques were used to study the chemical
transformations (curing, decomposition etc.) and morphological changes (melting ,
glass transition etc). Differential Scanning Calorimetric (DSC) studies were carried out
using a Mettler TA 3000 Thermal analysis system in conjunction with TC -lOA TA
processor and standard DSC-2920 analyser using aluminium sample pans The
temperature and heat flow calibrations were done by recommended procedures using
pure indium (melting point of 156.4"C and a heat of fusion). The heating rate
employed was 10'CI minute from RT to 300°C in air or nitrogen atmosphere, unless
otherwise specified. Glass transition temperature, extent of cure reaction.
temperatures at cure initiation and completion (Ti & T,) and peak reaction temperature
(T,,), were obtained from dynamic DSC curves. The calibration of the equipment was
done by calculating the enthalpy of reaction (AH) from sample mass (* 5mg) and area
under the exotherm using the melting transition of pure indium as the reference.

2.2.4.2 Thermo gravimetric Analysis

In thermogravimetric analysis, mass of the sample is recorded as a function of
temperature. Non-isothermal TG was performed in nitrogen atmosphere at a heating
Chapter 2 98

rate of 1O0C/minutefrom ambient to 700°C using TGA- SDT 2960 simultaneous TGA-
DTA -TA lnstruments5. The initial decomposition temperature (TI), temperature of
maximum thermal decomposition (T,) and temperature of completion of thermal
decomposition (Tc) as well as the char-yield were recorded from the TG thermograms.
The thermo balance has got a sensititvity of 2 micrograms and an accuracy of 1%

2.2.4.3 Thermo Mechanical Analysis

Thermo mechanical analysis was performed using a Perkin Elmer-model
TMA- 7 thermo mechanical analyzer5.The dimensional changes of the sample, when
subjected to programmed temperature variation, are measured as a function of
temperature. The quartz probe movement due to the thermal expansion of the sample
is detected by a linear variable differential transformer (LVDT). The displacement
sensitivity is 50nm and resolution is 3nm for the LVDT system. A heating rate of 5°C I
min. from RT to 300°C was used for the thermo-mechanical analysis.

2.2.4.4 Dynamic Mechanical Analysis

Isothermal and non-Isothermal DMA studies were performed for the cure
characterisation and cure optimization of the matrix systems, to evaluate visco-elastic
properties of the cured neat resins and laminates and for studying the morphology of
the matrix (neat or as blends) in composites. A Du Pont DMA 983 model instrument
was used for the purpose. For analysis in the dynamic mode a heating rate of 5"CI
min. was used from RT to 300"c6. Analysis was carried out at a fixed frequency of
I H z and the complex dynamic mechanical moduli (flexural storage (E') and loss (E')
moduli as well as shear storage (G') and shear loss (G') moduli) were recorded as
functions of temperature. The loss factor tan S = (E') I(E') = (G') I(G'). Low tan S
values represent elastic and resilient materials. The temperature corresponding to
'
maximum value of loss modulus, or tan S is taken as the T, of the material. Dynamic
Chapter 2 99

mechanical analysis was performed using specimens with dimension 40mm x 12mm x
3mm.

2.3 Preparation of Neat Resin Mouldings and Composites

Neat resin specimens were cast in a metallic mould 12cm x 10cm x 0.3cm. A
silicone mould release agent was applied prior to pouring the degassed resin mix in to
the mould. The epoxy resin and its blends were cured following the optimized time-
temperature schedule for the particular system.
The composites were prepared using silane treated E-glass and carbon fiber
Ifabric reinforcements. The matrix : reinforcement volume ratio was 40:60 in all cases
unless otherwise specified. The matrix blends were dissolved in AR acetone for
proper wetting of the reinforcement for the preparation of the prepregs. The prepregs
were dried overnight, cut and moulded in a hydraulic press of capacity 35 MPa and a
platen area of O.lmz and a maximum temperature range of 250°C to obtain the
laminates. The cure schedules for different systems are given in respective chapters.
Fracture energy test specimens of the laminate were prepared by introducing
a precrack of length 25.4 mm by inserting a thin teflon film at one end between the
14Ih and l5lh ply of a 28 ply laminate prepreg. The prepreg was laminated in the
hydraulic press and test specimens of 100mm x lOmm x 5mm dimension were cut for
the fracture toughness analysis.
The neat resin and composite specimens for different tests were cut using a
diamond wheel cutter as per the dimensions specified in the respective standard test
procedures.

2.4 Preparation of Syntactic foam Composites

Syntactic foam composites were prepared by mixing known weights of hollow
glass microballoon in the EPB matrix system so as to obtain foam composites with
different filler content. The composition of the foam composite was varied by using
Chapter 2 100

different types of fillers mixed in different proportions. The curing of the foam
composites was done as per the heating schedule optimized for the respective matrix
system, as described in the concerned chapter.

2.5 Mechanical Testing

2.5.1 Mechanical Testing of Neat Resin Castings
Universal testing machine lnstron-model 4202 was used for the mechanical
testing of the neat resins and composites. The mechanical properties under tension,
flexure, shear and compression and fracture toughness were determined using the
type of fixture, specimen size, strain rate and other test conditions mentioned in the
respective standard procedures. Dumb bell shaped specimens of 75mm length,
33mm gauge length, 6mm width and 2-3 mm thickness were used for tensile testing at
a crosshead speed of 5mWmin. as per ASTM D 638.

Tensile strength = PI b d (kglcm2) (2.1)

Where. P = Load at failure (kg)

b = Width of the specimen (cm)
d = Thickness of the specimen (cm)

% Elongation = Ux (2.2)
L,

Where, L, = Original length of the specimen

L, = Final length of the specimen.
Chapter 2 101

Compressive strength of the composite was determined using standard

specimens conforming to ASTM procedure mentioned in Table 2.2 and using a
crosshead speed of 2 rnml min.
Flexural strength was determined by applying flexural load on a rectangular
specimen using a three point bend fixture as per the standard ASTM procedure D
790. Rectangular specimens of length 100mm. width 10 mm and thickness 3-4 mm
were used. A span length of 80 mm was used and load was applied at a crosshead
speed of 2.3 mmlmin. The flexural strength was calculated from the peak load using
the equation

Flexural strength

Where P = Peak load (kg)

L = Span length (cm)
b = Width of the specimen (cm)
d = Thickness of the specimen (cm)

Fracture toughness (K,), of the neat resins (100mm x 35mm x 3mm) with an initial
crack length of lOmm was measured according to ASTM STP 240 at a crosshead
speed of Immlmin. Specimens were subjected to tensile load and load at the onset
of crack growth and subsequent failure was noted.

Where Q =1.99-0.41 (alb)+18.7(alb)~ - 3 ~ . 4 8 ( a l b ) ~

P = Load at onset of crack propagation (kg)
a = Initial crack length (cm)
Chapter 2 102

b = Width of the specimen (cm)

d = Thickness of the specimen (cm)

2.5.2 Adhesive properties of Neat resin

The adhesive strength of the matrix system was studied by determining its lap
shear strength (LSS). LSS specimens prepared according to the ASTM standard
procedure ASTM D -1002. The Lap shear strength was computed from the breaking
load (P),knowing the bonded area of the specimen.

Lap Shear Strength = Plab (kg/cm2) (2.5)

Where P = Load at failure (kg)

a = Width of the specimen (cm)
b = Breadth of the specimen (cm)

2.5.3 Mechanical Testing of Composites

The composite specimens cut from glass or carbon fabric reinforced
composites were subjected to different types of mechanical tests using the lnstron -
UTM model 4202, following the respective ASTM procedures. The properties studied
include flexural strength, compressive strength along the ply, fracture toughness,
inter-laminar and in-plane shear strengths, fatigue resistance and Stress relaxation

2.5.3.1 Flexural strength

Flexural strength of the laminate was determined as per ASTM D 790-'81.
Rectangular specimens of 130mm x 13mm x 6mm dimension with their ends resting
on two smooth cylindrical supports at a span of 80mm and center loaded in a 3-point
test fixture at a cross head speed of 2.3 mmlmin. The test specimens are subjected to
tension and compression simultaheously and the flexural strength values indicate the
Chapter 2 103

maximum stress that can be borne by the surface of fibers in bending mode. Load-
deflection curves were plotted during the test.

Flexural strength = -
3PL kglcrn2
2bd2

Where, P = Load at break point (kg)

L = Span length (cm)
b = Width of the specimen (cm)
d = Thickness of the specimen (cm)

A schematic of loading configuration of Flexural test is given in Fig. 2.1

I-------L-
SUPPORT SPAN

(Bl

Fig.2.1 Schematic of loading configuration of Flexural test

2.5.3.2 Compressive strength

Ability of the composite laminate to resist compressive forces applied parallel

to the ply direction was determined as per ASTM D 3410 using test specimens of
square cross section (5mm x 5mm) and 10 mm length. The compressive load was
Chapter 2 104

applied at a crosshead speed of 2 mmlmin and the compressive strength was

computed from the maximum load at failure, using the following equation.
P
Compressive strength = - (kg1cm2) (2.7)
bd

Where, P = Load at failure ( kg)

b = Width of the specimen (cm).
d = Thickness of the specimen (cm)

2.5.3.3 Fracture Energy

The fracture toughness which is a measure of the Inter laminar fracture
energy of the laminates was determined by in-plane sheai loading in mode II. End-
notch tlexural specimens (100mm x 10mm x 5mm) were subjected to testing at a span
of 85 mm and a cross head speed of 2mmlmin. as per ASTM D 30.02, 1987. The
Schematic illustration of mode II inter-laminar fracture test is given in Fig. 2.2

Fig 2.2 Schematic illustration of mode It inter-laminar fracture test (ENF)

The initial crack of length 25.4 mm propagates parallel to the direction of shearing and
failure of the specimen occurs when it reaches the point of loading. Load vs.
deflection curves were plotted and the compliance obtained from the slope of the load
Chapter 2 105

deflection curve and the maximum load at failure were taken for the computation of
the fracture energy using the equation

Fracture energy Glrc = 9aZPZC.gc (J lm2)

2b(2L3+3a3)
Where, a = Initial crack length (meter)
b = Width of the specimen ( meter)
L = Half span length (meters)
P = Load at failure (kg)
C = Compliance factor obtained from slope of load-
deflection curve (mlkg)
Gc = Gravitational constant (m1s2)

2.5.3.4 Inter laminar shear strength

The inter laminar shear strength of the composite specimens was tested by
short beam shear test (SBS) method according to ASTM D 2344-76 by three point
bending. A crosshead speed of 1.3 mmlminute and a span to depth ratio of 5 was
used for testing. Repl~catetests were conducted on 4-5 specimens in each case and
average value was taken. Schematic loading configuration of short beam shear (SBS)
test is given in Fig. 2.3. The interlaminar shear strength was calculated from the peak
load corresponding to the interlaminar failure of the specimen using the following
equation.

Where P = Breaking load (kg)

b = Width of specimen (cm)
d = Thickness of specimen (cm)
Chapter 2 106

Fig. 2.3 Schematic of loading configuration of short beam shear (SBS) test

2.5.3.5 In-plane shear Test

The in-planel interfacial shear test is performed according to the standard
ASTM method D-3846 (95) employing a notched rectangular specimen shown in
Fig.2.4

' L
Fig 2.4
lrsw
IS.NW
- -
In- plane shear test specimen

The load required for the shear failure of the area between two centrally located
notches machined half way through its thickness is measured by subjecting the
Chapter 2 107

specimen to tensile loading in the UTM and the in-plane shear strength is calculated
using the following equation

In-plane shear strength =

P
- (kglcm2) (2.10)
bd

Where, P = Maximum load at failure in kg

b = Width of the specimen in cm.
d = Length of the failed area in cm

2.5.3.6 Fatigue Test

Fatigue resistance was evaluated by conducting the extension cycling test

using the Universal testing machine at a fixed strain level, and monitoring the load
decay in the specimen after a specified number of cyclic loadings. This technique is
used for the comparison of the fatigue resistance of different types of composites. The
test was carried out as per the standard ASTM procedure mentioned in Table 2.2 and
the extent of fatigue damage was computed from the decay of stress after fixed
number of cycles, and expressed as the percentage of the initial stress.

2.5.3.7 Stress relaxation

The stress relaxation test was carried out on composite specimens of 5mm x
5mm cross section and 150 mm length. The strain level of 2% was selected for all
stress relaxation tests. A gauge length of lOOmm and an initial loading rate of 10 mm/
min. were used for the analysis. The load was monitored as function of time. The
relaxation modulus at zero time (L)and that at different time intervals (E,) were
computed from the load values corresponding to the respective time intervals and the
cross sectional area of the specimen.
Chapter 2

2.6 Physical property evaluation

2.6.1 Fracture Surface Analysis of Composites

The morphology of the fractured surfaces was analysed using scanning

electron microscopy (SEM). A Stereoscan CAMBRIDGE Instruments model Mk 250
was used for the same. The specimen surface was made electrically conducting by a
conductive layer of gold, coated using the plasma vapor deposition technique in a FINE
COAT ION S P ~ JFC-ilk.
R A fine electron beam is scanned across the surface in
synchmnisation with the beam in a cathode ray tube. The signal produced by the
scattered electrons modulates the beam in the cathode-ray tube producing the
image4.
2.6.2 Water absorptlon
The water absorption characteristics of the composites were determined from
the weight of water absorbed by the composite specimen of specifd dimension
(20mm x 4mm XlOmm), immened in boiling water for specified period (2 hours)as per
the standard ASTM procedure D-570-98.

2.6.3 Constituent content

The constituent content of the composite was determined by physically
removing the matrix by digestion of the same in a suitable acid or by ignition, leaving
the reinforcement unaffecw. The matrix digestion! ignition was carried out as per
the standard ASTM procedure D-3171-99 and the constituent content was computed
from the weight of the composite specimen before and after matrix digestion.

2.6.4 Void content

The void content in the composite was computed from the densities of the
individual components and the fiber Imatrix content in the composite. The densities of
the cured matrix and the reinforcement were determined as per the standard ASTM
Chapter 2 109
- -- -

procedure 0-792-82. The fiber- content is determined in accordance with ASTM D-

3171-99 12584-82.The void content is determined following the ASTM test procedure
D-2734 test method A, using the equation

Where. Vc = Void content (volume %)

Td= true density of the composite
Md= measured density of the composite.

2.7 References
1 C. Gouri, C. P. R. Nair, R. Ramaswamy, Polym. Int., 50, 404 (2001)
2 C. P. R. Nair, Tania Francis, J. Appl. Polym. Sci., 74, 3366 (1999)
3 C. P. R. Nair, T. V. Sebastian, S. K. Nema, K. V. C Rao. J. Polym. Sci.,
Chemistry. 24, 1109 (1986)

4 Instruction manual- Waters model-2690 Alliance Gel Permeation

Chromatograph Waters Associates, USA. (1989)

5 Perkin Elmer Users Manual 7 Series I Unix TMA 7 Thermo mechanical

Analyser (1989)

6 Dupont Instruments DMA 983 Operators Manual (1989)

7 R. Bruce prime, Thermal characterisation of polymeric Materials, Ed. E. A.

Turi, Academic press, znd Ed., 2, 1464 (1997)

8. Fluke Instrumentation Catalogue, Section. 5 (1996)